Polyazo dyestuffs



United States Patent Application December 13., 1954, Serial No. 474,990

Claims priority, application Switzerland December 24, 1953 7 Claims. (Cl. 260-173) No Drawing.

This invention relates to polyazo dyestufis. According to the present invention, valuable new polyazo dyestuffs are obtained when 1 mol of an aminobenzoylaminodisazo compoundof the formula wherein R1 and R2 represent radicals of the benzene or naphthalene series free from hydroxy, nitro and amino groups and which together contain at least two sulfonic acid groups, R3 is a radical of the benzene series 'free from hydroxy, nitro and amino groups, one x is an amino group, the other x: being an atom of hydrogen or a halogen or'an alkyl or analkoxy group, and the azogroup is inpara-position to the N=N- group as well as to the NH--CO- group, is diazotized, and the diazo compound is coupled with 1 mol of ahydroxynaphthalenesulfonic acid which may contain an acylamino group, preferably with 1 mol of a Z-acyIamino-S-hydroxynaphthalene-7-sulfonic acid or a 2-acylamino-8-hydroxynaphthalene-6-sulfonic acid.

The aminobenzoylaminodisazo compounds of Formula I may be prepared by condensing an aminodisazo com.- pound of the composition wherein R1,"R2' and R3 have the meanings hereinbefore given and the two --N=N groups are para-positioned, with:a nitrobenzenecarboxylic acid halide of the formula Rz-NHz which couples in para-position to the amino lice group, diazotizing the resulting aminomonoazo compound and coupling the diazo compound with an amine of formula Rs-NHz which couples in para-position to the amino group. In this case also the symbols R1, R2 and R3 have the meanings given above.

The new polyazo dyestufis ofthe present invention conform to the general formula wherein R1, R2 and R3 have the meanings given above, w represents a hydrogen atom or an acylamino group, n is 1 or 2, and the azo group is in para-position to the N=N- group as well as to the -NHCO- group.

Specially valuable new pol-ya zo dyestutfs are those which correspond to the general formula wherein R1, R2, R3 and azo have the meanings given above, and one of the substituents z represents a hydrogen atom and the other an NI-I-acyl group, where acyl represents the radical of a carboxylic acid.

Suitable amines of theformula R1NH2 serving for the production of the aminodisazo compounds (II) according to the above process are, for example, aminobenzene-monoand disulfonic acids, aminomethylbenzenesulfonic acids, aminohalogenbenzenesulfonic acids and aminonaphthalenemonoand disulfonic acids. Rep resentative of the Rz--NH2 amines are, for example, 1-amino-2- or 3-methylbenzene, 1-amino-2,5-dimethylbenzene, l-amino-Z- or 3-methoxybenzene, l-amino-Z- methoxy-S -methylbenzene, l-amino-2,5-dimethoxyor diethoxybenzene, 1-amino-3acetylaminribenzene, l-aminonaphthalene and l-aminonaphthalene-G- or 7-sulfonic acid. Finally, as illustrative of the R3NH2 amines there are mentioned, by way of example, the aminobenzenes listed under R2-NH2. Very valuable aminodisazo compounds (II) are also obtained by diazotizing an aminobenzene disulfonic acid, for example 4-amino-l,l'-azobenzene-3,4'-disulfonic acid, and coupling the diazo compound with one of the above defined amines of the formula R3-NH2.

A large number of nitrobenzene carboxylic acid halides (III) are suitable for condensation with the aminodisazo compounds (II). These'include 3- or 4- nitrobenzoyl chloride, 3-nitro-4-methoxybenzoyl chloride, f 3-methyl- 4 nitrobenzoyl chloride, 3-chl'oroor -bromo-4.-nitrobehz0?l chloride'and the'corresponding benzoyl bromides, etc.

Representative of the hydroxynaphthalenesulfonic acids, some of which have an acylamino group, are l-hydroxynaphthalene-3- or -4-sulfonic acid or -3,6-disulfonic acid, 2-hydroxynaphthalene-4 or -6- or -8-sulfonic acid or -6,8- disulfonic acid, l-acetylaminoor -benzoylamino-5-hy- SOaH OH: I l

droxynaphthalene-7 sulfonic acid, l-acetylaminoor -benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid, etc. Preferred species are 2-acetylaminoor -propionylaminoor -crotonylaminoor -benzoylaminoor -cinnamoylamino-S-hydroxynaphthalene-7-sulfonic acid and the corresponding 2-amino-S-hydroxynaphthalene-6-sulfonic acids, 2-(3- or -4'-arnino)- or -(3-methyl-4- amino)- or -(3'-amino-4'-methoxy)-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid and the corresponding 2-amino-8-hydroxynaphthalene-6-sulfonic acids, Z-carbomethoxyaminoor -carbethoxyaminoor -carbopropoxyaminoor -carbobutoxyaminoor -carbo-(2'-ethoxy)- ethoxyamino-S-hydroxynaphthalene-7-sulfonic acid and the corresponding 2-amino-8-hydroxynaphthalene-6-sulfonic acids and finally -hydroxy-7-sulfonaphthalene-Z- carbamic acid-(4-acetylamino) -phenylamide.

The new polyazo dyestufis according to the invention dye cotton and fibers of regenerated cellulose in orange, red to reddish-brown, light-fast and dischargeable shades. If the azo components possess a primary amino group they may be diazotized on the fiber and coupled with suitable azo components such as 2-hydroxynaphthalene. Through such an after-treatment the fastness to Water as well as to washing of the dyeings is considerably increased.

The following examples illustrate the invention in non-limitative manner. The parts given are by weight, the percentages are by weight and the temperatures are in degrees centigrade.

SOsH CH:

O H I l EXAMPLE 1 59.4 parts of the aminobenzoylaminodisazo compound, obtained by the acid coupling of diazotized 4-amino-1,1- azobenzene-3,4-disulfonic acid with 1-amino-3-methylbenzene, condensing the resulting aminodisazo compound with 4-nitrobenzoyl chloride, and then reducing the nitro group to the amino group, are dissolved in 600 parts of water adjusted to neutrality by the addition of sodium hydroxide. 7 parts of sodium nitrite are added to the resulting solution, and this is slowly introduced into a mixture of 45 parts of 30% hydrochloric acid and 100 parts of ice in such manner that the final temperature of the mixture is 5-10. When the diazotization is finished, which is the case after 4-6 hours, the diazo suspension is allowed to flow within 30 minutes at into a neutral solution of 34.3 parts of 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid and 4 parts of sodium hydroxide in 300 parts of water. At the same time,there is added to the coupling mixture sufiicient sodium bicarbonate to maintain the pH of the solution constant at between 6 and 7. Coupling takes place very quickly; the solution containing the formed trisazo dyestufl completely dissolved therein is then heated to 70, and the dyestuff is salted out, filtered and dried.

5 The new dyestufi corresponds to the formula 5 and is a red powder which dissolves in water with a red coloration and in concentrated sulfuric acid with a blue coloration. It dyes cotton and fibers of regenerated cellulose in yellowish-red shades which have good fastness to light and are dischargeable.

EXAMPLE 2 60.8 parts of the aminodisazo compound, obtained by the acid coupling of diazotized 4-amino-1,1'-azobenzene- 3,4-disulfonic acid with 1-arnino-3-methylbenzene, condensing the resulting aminodisazo compound with 3- methyl-4-nitrobenzoyl chloride, and then reducing the nitro group to the amino group, are .dissolved in 750 parts of water adjusted to neutrality by the addition of sodium carbonate. 7 parts of sodium nitrite are added to the resulting solution, and this is slowly introduced into a mixture of 45 parts of 30% hydrochloric acid, 120 parts of ice and 30 parts of water in such manner that the final temperature of the mixture is 5-10". When the diazotization is finished, the diazo suspension obtained is allowed to flow within minutes into a neutral warm solution, at 40, of 37.2 parts of 2-(3-methy1-4'-amino)- benzoylamino-S-hydr0xynaphthalene-7-sulfonic acid and 4 parts of sodium hydroxide in 400 parts of water. At the same time there is added to the coupling mixture 40 sufficient sodium carbonate to maintain the pH constant at between 6 and 7. When the coupling is finished, the solution containing the formed trisazo dyestufr" is heated to 70, the dyestutf is salted out, is filtered and then is dried.

The new trisazo dyestufi corresponds to the formula s HOzS The table which follows gives further trisazo dyestuffs which likewise may be obtained as described in Examples 1 and 2. They are characterized by The aminoazo compounds (II) in column (A),

The nitrobenzenecarboxylic acid halides (III) in column (B), and

The hydroxynaphthalenesulfonic acids used as azo com ponents in column (C). I

In column (D) is given the type of trisazo dyeing used,

and in column (B) the shade of dyeing on cotton given by diazotizing the same and coupling with 2-hydroxynaphthathe tnsazo dyestufis and/ or developed on the fiber by lcnc.

Table Example 3 4-amino-1,1-azobenzene-3,4- s-nitrobenzoyl chloride 2 acetylamlno hydroxy .Direct dyestuflf reddish orange.

disulfonic acid 1- naphthalene-7-sulionic.acid. amino 2 methoxy 5 methylbenzene. Y Y 4 4 amino 1,1 azo benzene 4-nitr0be11zoy1 chloride 2-cinnamoylamino-5-hydroxy- .do scarlet red.

3,4-disulfonic acid 1- naphthalene 7 sulionic amino-2,5-dimethylbenzene. acid. 5 4-amino 1,1 -azobenzene-3,4- 3-chloro-4-nitrobenzoyl chlo- 2 benzoylamino 8 hydroxydo bluish red.

disulfonic acid amiride. naphthalene-fi-sulfonic acid. nobenzene. 6 4 amino 1,1 azobenzene -3,4- 4-nitrobcnzoyl bromide 2 hydroxynaphthalene 6 5111- do yellowish red.

disulfonic acid 1 a ionic acid. mine'3-acetylamino-benzene. 7 4-ami11o 1,1'- azobenzene-3,4- 3-nitro-4-cthoxybenzoyl chlo- 1 hydroxynaphthalene 3 sul- .do Do.

disulfonic acid 1 aride. fonie acid. mine-2,5-dimethylbenzene. 8 4-ami11o-1,1-azobenzene-3,4'- 4-m'trobenzoyl chloride 1 hydroxynaphthalene 3,6 do scarlet red.

disulfonic acid 1 adisullonic acid. mino-S-methylbenzene. 9 do da 2 crotonylamino 8 hydroxydo bluish red.

naphthalene 6 sulfonic acid.

10- n n 2 (4 amino) henzoylamino Developed dyestufiscarlet red.

5 hydroxynaphthalene 7 sulionic acid. 11 d0 3 nitro 4 methoxybenzoyl 2 (3 amino 4' methoxy) do Do.

chloride. benzoylamino 5 hydroxy naphthalene-7-sulfouic acid. 12 do 4-nitrobenzoyl chloride 2 (4' amino) benzoylamino do bluish red.

8 hydroxynaphthalene 6 sulionic acid. 13 do n 2- carbomethoxy amino 5 -hy- Direct dyestufi yellowish red.

drbirynaphthalene 7 sulfonic ac 14 dn dn 2 carbo (2 ethoxy) ethoxydo D0.

amino 5 hydroxynaphtha- 1ene-7-su1l'onic acid. 15 do S-nitrobenzoyl bromide 5 hydroxy 7 sulfonaphthado reddish orange.

' lene 2 carbaminic acid (4-- acetylaminog-phenylamide. 16 4-amino-1,1' -azobenzenP-3,4- 3 methyl 4 nitrobenzoyl 2 (4 amino benzoylamino- Developed dyestufi. Sc rle red.

disulfonic acid 1 achloride. fi hydroxynaphthalene-7-su1- mino-2,5-dimethylbenzene. fonie acid. 17 4-amino-1,1 -azobenzene-3,4- 4-nitrobenzoyl chloride 2 (3 amino) benzoylaminodo Do.

disulfom'c acid 1 a- 5-hydroxynaphthalene-7-sulmino 2 methoxy 5 methylionic aci benzene. 18 do 3 bromo 4 nitro benzoyl- 2- (3 -methyl 4 ammo) -bendo bluish red.

chloride. zoylamino 5 hydroxynaphthalene-7-sulfonic acid. 19 l-aminobenzenci-sulfonic acid 4-nitrohenzoyl chloride 2- propionylamino 5-l1ydroxy- Dir t dyestufi red.

l-aminonaphthalenenaphthalene-7-sulfomc acid. d-sulionic acid l-amino-3-methylbenzene. 20 do dn 2 (4 amino) benzoylaminodo bluish red.

5-hydroxynaphthalene-7 -su1- ionic acid. 21 dn do 1 hydroxynaphthalene 4 suldo red.

ionic acid. 22 1-amin0benzenc-4-suli0nic acid 3 -ethyl-4 -nitrobenzoyl chloz-cinnamoylamino-s-hydroxydo brownish red.

l-aminonaphthaieneride. naphthalene-(rsulfonic acid. 7-sulfonic acid i-amino 2 methoxy 5 methylbenzene. 23 1-aminobenzene-2,5-disulfonic 4-nitrobenzoyl chloride 2 hydroxynaphthalene 8 suldo red.

acid l-aminonaphionic acid. thalene 1-amino-3- methylbenzene. 24 l-amino 2,4 dimethylbenzenedo 2 benzoylamino 5 hydroxydo Do.

G-Sulionic acid l-aminaphthalene-7-sulfonic acid. nonaphthalene-6-sulfonic acid 1-amino-3-methylbenzene. 25 1 amino 2 chlorobenzene 4- -.-..do 2 (4' methyl) benzoylaminodo brownish red.

sulionic acid l-ami- 5 hydroxynaphthalene-7-sulnonaphthalene-fi-sulfonic acid ionic acid. l-amino-2-methoxy-5- mcthylbenzene. 26 2 aminonaphthalene 6,8 dido 2-hydroxynaphthalene-3,6-dido scarlet red.

sulfonic acid aminosulionic acid. benzene 1-amino-3- methylbenzene. 27 2-aminonaphthalene 6,8 disul- 3-nitrobenzoyl chloride 2 crotnnylamino 5 hydroxydo yellowish red.

ionic acid l-aminonaphthalene-7-sulionic acid. 3-methylbenzene l-aminoB-methylbenzene. 28 do 4-nitrobenzoyl chloride 2- (4 amino) -benzoylamino-5- Developed dycsmfi. scarlet red.

hydroxynaphthalene 7 sulfonic acid. 29 2-aminonaphthalene 6,8 disul- 3 methoxy 4 nitrobcnzoyl 2-(3-methoxy 4' amino) bendo bluish red.

ionic acid l-aminochloride. zoylalnino 5 hydroxynaph- 2 methoxy 5 methylbenthalene-7-sulfonic acid. zene 1-arnino-3-methylbcnzene. 30 Z-aminonaphthalene 4,8 disul- 4-n1trobenzoyl chloride 8-hydroxy-6-sulfonaphthalene- 2- Direct dyestuii red.

fonic acid l-amino-3- methylbenzene l-amino-limcthylbenzene.

carbaminic acid-(4-acetylamino) -phenylamide.

Following are the formulae of representative dyestufis of the foregoing table:

Example Example SOIH HOiS OH: CH:

EXAMPLE 31 100'parts of cotton are introduced 'into .a dyebath comprising 0.5 part of the trisazo dyestufi robtainedac cordingto Example 1, and 1 part of anhydrous sodium carbonate. The dyebath is slowly brought to the boil, then parts of anhydroussodium sulfate are added and the bath slowly cooled to about 70. The dyed cotton is Well rinsed with cold water and then dried.

EXAMPLE 32 100 parts of cotton are dyed as described in the'foregoing example with 0.5 part of the trisazo dyestuff obtained according to Example 2. The well-rinsed dyed material is treated in a cold bath with 2 parts of sodium nitrite and 5 parts of concentrated hydrochloric acid, again rinsed for a short while with cold water and then introduced into a cold developing bath .containing 1 part of Z-hydroxynaphthalene dissolved by means of 1 part of aqueous sodium hydroxide solution. The dyed material is digested for /2 hour inthe developing bath, after which it is thoroughly rinsed and finally dried.

Having thus disclosed the invention, what is claimed 1s:

1. A polyazo dyestuff which corresponds to the formula wherein each of R1 and R2 stands for a member selected from the group consisting of substituted and unsubstituted radicals of the benzene and naphthalene series, the substituents being chosen from the class consisting of chlorine atoms, lower alkyl, lower alkoxy and sulfonic acid groups, R3 stands for a member selected from the group consisting of substituted and unsubstituted radicals of the henzene series, the substituents being chosen from the class consisting of lower alkyl, lower alkoxy and acylamino Example 27 groups, the acyl group being carboxylic acid acyl, R4 stands for a member selected from the group consisting of substituted and unsubstituted radicals of the benzene 01 Boss Boss- NH-C 001m,

series, the substituents being chosen from the class consisting of chlorine and bromine atoms, lower alkyl and lower alkoxy groups, w stands for an acylamino group, the acyl group being carboxylic acid acyl, it stands for one of the numerals 1 and 2, and wherein --azois linked in para-position with respect to azo' and to NHCO, and wherein azo is linked in ortho-position with respect to --OH and is linked in one of the paraand meta-positions with respect to --NHCO--.

2. The polyazo dyestufi which corresponds to the wherein each of R1 and R stands for a member selected from the group consisting of substituted and unsubstituted radicals of the benzene and the naphthalene series, the substituents being chosen from the class consisting of chlorine atoms, lower alkyl, lower alkoxy and sulfonic acid groups, R3 stands for a member selected from the group consisting of substituted and unsubstituted radicals of the benzene series, the substituents being chosen from the class consisting of lower alkyl, lower alkoxy and acylamino groups, the acyl group being carboxylic acid acyl, R4 stands for a member selected from the group consisting of substituted and unsubstituted radicals of the benzene series, the substituents being chosen from the class consisting of chlorine and bromine atoms, lower alkyl and lower alkoxy groups, one 2 stands for a hydrogen atom, and the other z stands for an acylamino group, the acyl group being carboxylic acid acyl, and wherein azo"- is linked in para-position with respect to ,azo' and to NHCO, and wherein azo"' is linked in one of the paraand meta-positions with respect to -NH-CO.

3. The polyazo dyestufi which corresponds to the formula SOaH om HOaS NHO 06 4. The polyazo dyestufr which corresponds to the formula 5. The polyazo dyestufi which corresponds to the formula 6. The polyazo dyestufi which corresponds to the formula 7. The polyazo dyestuflf which corresponds to the formula HOaS References Cited in the file of this patent UNITED STATES PATENTS 2,659,721 Bossard et a1 Nov. 17, 1953 FOREIGN PATENTS 292,086 Switzerland Oct. 16, 1953 

1. A POLYAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 